Brominated oils



United States Patent of Illinois No Drawing. Filed Jan. 24, 1%4, Ser.No. 339,889 6 Claims. ((11. 260-348) The present invention is directedto the manufacture of brominated oils; more particularly, it isconcerned with the manufacture of brominated oils of much improvedstabilities.

Brominated oils are used to adjust the specific gravity of citrus oilsso that a flavoring emulsion can be made which will stay suspended inbeverages. As well as flavor, the emulsion provides cloud to give thedrinks good appearance.

Citrus oils used as flavoring agents are insoluble in water and have aspecific gravity of about 0.85, while they are used in beverages with aspecific gravity of about 1.0 for dietetic drinks or about 1.03 to 1.06for sugar-sweetened drinks.

Brominated oils are dense liquids which can be blended with the citrusoils to balance the specific gravity with respect to the finished drink.From this oil mix, an emulsion can be prepared which will have goodstability in the beverage.

Unfortunately, brominated oils suffer from the grave disadvantage ofhaving low stability; in fact, the stability of known brominated oils isso low that manufacturers routinely mark their product as having alimited shelflife because it will gradually degrade when exposed to airor normal summer temperatures for prolonged periods of time. Upondegradation, color, acidity and/or rancidity develop and obviously theproduct is no longer acceptable to the food and beverage industries.

It is thus an object of the present invention to provide a bromine-tedoil oat high stability. It is a particular object to provide a method ofmanufacturing a brominated oil with high stability against formation ofcolor and acids. It is 'a further object to provide a brominated oilwith an extended shelf-life and which does not develop discoloration orincreased acidity upon storage.

These and other objects are accomplished by the method of the presentinvention whereby an unsaturated oil, in which 8797% of the initiallypresent canbon-to-c-arbon unsaturations are brominated, is treated withan epoxidizing agent such as peracetic acid, periormic acid, or otherorganic per-acids, until substantially all doublc-bonds are saturated.The excess acid is then neutralized by the addition of a base and theformed insoluble by-prod-ucts are removed by filtration, centrifugation,or other separation techniques.

In a general embodiment of the present invention, an unsaturated oilsuch as sesame oil, safilower oil, cottonseed oil, olive oil, corn oil,soybean oil, or a mixture of such unsaturated oils, is treated withbromine whereby the amount of bromine added is calculated in such a waythat an unsaturation of about 343% of the initial unsaturation remainsin the oil. The treatment with bromine is carried out at a temperaturebetween 10 and 30 C. under agitation. Ordinarily, the bromination takesplace almost instantaneously and the completion of the reaction iseasily detectable by the disappearance off the red color of the freebromine. Brominations of unsaturated oils are described in more detailin the Journal of Laboratory and Clinical Medicine, volume 16, pages 36if, of 1930, and numerous more recent publications. However, the priormethods require neutralization at the end of the bromination, while inthe method of the present application, neutralization is neitherrequired nor desired at this point. The reaction mixture is directly3,187,019 Patented June 1, 1%65 treated with 1-3% by weight ofcommercial 40% per.- acetic acid or a similar amount of another organicperacid at a temperature between 0 and 40 C. The mixture is stirred :forat least one hour at this temperature and the excess acid is thenremoved by neutralization with a base or an alkaline agent such assodium carbonate, potassium carbonate, calcium hydroxide, and the like.Preferably, an alkaline agent is selected which has the capability offorming a hydrate. This agent is then added in its anhydrous form sothat any water formed as by-product is absorbed and gets eliminated inthe subsequent removal step for the salt. After filtration, the oil isvery light-colored, stabilized against acid and color development, andbland in taste like the original unsaturated oil.

For the purpose of illustration, reference is made to the followingexample:

Example To 125 grams of sesame oil of iodine value is added 83 grams ofbromine under thorough agitation while the temperature is maintainedbelow 30 C. by means of external cooling. After the red color of thebromine disappears, 4 grams of 40% commercial peracetic acid is addedand the mixture is stirred for 2 hours at room temperature. Thereafter,the excess acid is removed by the addition of suflicient sodiumcarbonate to neutralize the mixture. The reaction mixture is thenfiltered and a pale-yellow pure oil is obtained. This oil is stable todiscoloration and the formation of acids for more than six months, asshown by frequent color inspections and titrations with dilute sodiumhydroxide.

The above outlined process can also be carried out in the presence of asolvent but the use of such a solvent is not recommended because thesubsequently necessary elimination thereof produces additional costs andwith most solvents, a last trace is almost impossible to remove, leavingan objectionable odor in the oil.

Substantially the same stability can be achieved by substituting thesesame oil in the above example with commercially available cottonseed,corn, olive, soy-bean or safflower oil. In all cases, the color remainsthe same over a period of six to twelve months, while a nonepoxidizedbut neutralized sample will turn dark enough to block light transmissionwithin days or a few weeks. In all cases, the acidity determined bytitration with 0.1 N aqueous sodium hydroxide remains constant for atleast six months, while acid formation is apparent Within several weeksfor the corresponding control samples which are 'brominated as above andneutralized but not epoxidized.

Actually, the amount of bromine for the bromination of the initialvegetable-oil does not have to be calculated for a substantialdeficiency to produce a brominated oil with 3-13% of the initialunsaturation retained, since it is known that a complete saturation isgenerally somewhat more difiicult to achieve. Ordinarily, a slightlyundercalculated equimolar amount will give excellent results. Actually,many of the commercially-available brominated oils fall into the aboverange of 313% re maining unsaturation which is reflected by an iodinenumber of from about 3-10; they represent excellent starting materialsfor the process of this invention.

It will be obvious to those skilled in the art that the estimatedshelf-life of the birominated oils according to the present invention isof great importance [for the food and beverage industries where thesebrominated oils have been used in the past to blend with essential oilsin order to attain a specific gravity as close as possible to thespecific gravity of the liquid with which they are to be mixed asflavoring agent. To attain any desired specific gravity, the proportionsof the brominated/ epoxidized oil of the present invention and theessential oil are calculated by the convenient and simple way of thePearson-Square method.

For the purpose of this invention, almost any organic per-acid can beused for the epoxidation of the remaining double-bonds of theunsaturated oils. Among the most economical organic pereacids usetfiulfor this purpose are performic, peracetic, perpropionic, .perbutyric,perbenzoic acids, and the like. Whatever acid is used for this purpose,it is preferably selected in such a way that it is Water-free. The usedper-acid as Well as the normal carboxylic acid from which it is derived(and which is (formed again as a by-product) should be odorless,colorless and pure, and preferably of low toxicity even though the acidresidue is subsequently eliminated by the neutraliz ation andfiltration. The amount of the per-acid to be used should be at least0.3% by weight of the brominated oil but 'it may be as high as 5% oreven although no advantage is gained in using more than about 2% of thepure per-acid by weight of the brominated oil.

Others may practice the invention in any of the numerous ways whichwill-be obvious to those skilled in the art by thepresent disclosure.All such practice of the invention is considereda part hereof providedit falls withinthe scope of the appended claims. I claim:

1. The process of producing a stable oil essentially comprising thesteps of adding at least 0.3% by weight of an organic per-acid to abrominated vegetable oil in which 87-97% of the initially present doublebonds are saturated with bromine,

mixing said components at a temperature between 0 and 40 C. for a periodof at least one hour, neutralizing said mixture, and

removing the immiscible lay-products from said mixture. 2. The processperacetic acid.

3. The processof claim 1 wherein the mixture is neutralized with analkali metal carbonate.

' 4. The processiof claim 1 wherein the formed byproduct is removed byfiltration.

5. A brominated vegetable oil wherein 87-97% of the initially presentunsaturation -is saturated with bromine and substantially all remainingMind. 7

6. An oil according to claim 5 wherein the initial unsaturated oil isselected from the group consisting of sesame oil, olive oil, corn oil,soybean oil, safflower oil and cottonseed oil.

of claim 1 wherein said per-acid is IRVING MARCUS, Primary Examiner.

NICHOLAS s. RIZZO, Examiner.

double-bonds are epox-

1. THE PROCESS OF PRODUCING A STABLE OIL ESSENTIALLY COMPRISING THESTEPS OF ADDING AT LEAST 0.3% BY WEIGHT OF AN ORGANIC PER-ACID TO ABROMINATED VEGETABLE OIL IN WHICH 87-98% OF THE INITIALLY PRESENT DOUBLEBONDS ARE SATURATED WITH BROMINE, MIXING SAID COMPONENTS AT ATEMPERATURE BETWEEN 0* AND 40*C. FOR A PERIOD OF AT LEAST ONE HOUR,NEUTRALI2ING SAID MIXTURE, AND REMOVING THE IMMISCIBLE BY-PRODUCTS FROMSAID MIXTURE.